Gael ludwig mullee



UNITED STATES PATENT OFFICE.

CARL LUDXVIG MULLER, OF LUDWIGSHAFEN-ON-THE-RHINE, BAVARIA, GER-- MANY,ASS-IGNOR TO THE BADISOHE ANILIN AND SODA FABRIK, OF.

MANNHEIM, GERMANY.

MANUFACTURE OF SULPHONATED PURPLE DYE-STUFFS FROM BASIC ROSANILINE.

SPECIFICATION forming part of Letters Patent No. 353,264, dated November23, 1886.

Applicati n filed September 25, 1886. Serial No: 214,547. (Specimens.)

To aZZ whom it mayconcern:

Be it known that I, CARL LUDwIor Mi'ILLER, a subject of the King ofBavaria, residing at Ludwigshafenbathe-Rhine,in the Kingdom of Bavariaand Empire of Germany, have invented new and useful Improvements in theManufacture of a Sulphonated Purple Dye- Stuff or Coloring-Matter fromthe Basic Rosaniline Derivative Resulting from the Condensao tion'ofTetraethyldiamidobenzophenone with Methyldiphenylamine, of which thefollowing is a specification.

This invention relates to the manufacture of a sulphonated purpledye-stuff or coloring- 1 5 matter from the basic rosaniline derivativeresulting from the condensation of tetraethyl diamidobenzophenone withmethyldiphenylamine.

In carrying out my invention I take about forty parts, by weight, oftetraethyldiamidobenzophenone and mix the same intimately with 22.5parts, by weight, of methyldiphenylamine and three parts, by weight, oftoluol. I then quickly add twelve parts, by weight, of oxychloride ofphosphorus. The mixture thus produced is then heated under constantagitation until its inside temperature has reached about 100 centigrade,at which temperature it is to be kept during the space of about tenhours. The bronze-colored melt thus obtained is boiled with about thirtyparts of water until the toluol is evaporated; then common salt isadded. The resulting acid and saline solution, after being allowed tocool down and settle, is then separated from the undissolved residue bydecantation. The said undissolved residue is afterward exhausted withboiling water. The dark-purple solution thus obtained is filtered at aboiling-heat 4 and precipitated while hot with common salt. Theresulting precipitate is washed and dried. In orderto convert the basicrosauiline derivative thus produced (and which, according to itschemical composition, may be called ate- 4 5 t'raethyl methylphenylpararosaniline into my new sulphonated coloring-matter, possessing acidproperties, and therefore capable of dyeing in an acid bath,-the knownmethods of sulphonization may be employed. Practical the followingcharacteristics:

results are obtained by treating the said basic coloring-matter withfuming sulphuric acid at a temperature requiring to be regulatedaccording to the strength of the sulphuric acid employed. Theaction ofrectified sulphuric acid produces inferior results on account of 5 itsrequiring the assistance of a temperature exceeding 100 centigrade, andthus liable of injuring the coloringmatter, while fuming sulphuric acideffects the desired sulphonization at a considerably lower temperature,and even without any external application of heat.

As an example, I proceed as follows: About one part, by weight, of thebasic rosaniline derivative (produced, as before described, bythecondensationoftetraethyldiamidobenzophenone with methyldiphenylamine)is added in the state of a dry powder in the cold, and in very smallportions at a time, to about four to five parts, by weight, of fumingsulphuric acid containing about thirty per cen- 7o tum of free sulphuricanhydride. The acid mixture is externally surrounded with ice, and careis taken to prevent any rise of its temperature beyond 10 centigrade.The acid melt thus obtained, after being first allowed to stand at atemperature of about from 15 to 20 centigrade during the space of abouttwelve hours, is afterward carefully diluted with about twenty times itsown volume of ice-cold water. .Part of the free sulpho-acidprecipitates, and the sulphoacid which remains in solution separatescompletely on partial neutralization with caustic-soda liquor. Theprecipitated coloring-matter is separated from the solution bydecautation, then dissolved in warm dilute ammonia, and,after cooling,filtered and precipitated with common salt. The flocculent precipitatethus obtained is then filtered, pressed, and dried. v

The sulphonated dye-stuff or coloring-matter produced in the usualmercantile form of a sodium salt, as before described, presents It hasthe appearance of a dark-blue powder, possessing a bronze-like luster,easily soluble in water with 9 5 a bright bluish-purple color. By theaddition of caustic alkalies the said purple color of the aqeuoussolution becomes gradually destroyed,

but is restored upon neutralizing the free alkali with a mineral ororganic acid. Rectified sulphuric acid dissolves the dye-stuff with ayellowish-red color, which upon the addition of water turns blue, adark-blue precipitate of the free sulpho-acid being formed at the sametime. Strong hydrochloric acid produces a red-brown solution. Bysubmitting an intimate mixture of the dye-stuff with lime to destructivedistillation a basic oil distills over possessing a characteristicdisagreeable smell, and partly insoluble in diluteuhydrochloric acid,the insoluble portion of the same developing a blue color in thepresence of nitric acid,

The dyeing properties of my new sulphonated purple resemble those of thewell-known sulphonated derivatives of aniline-blue generally known underthe name of alkali blue, inasmuch as it is capable of becoming fixedupon animal fiber in an alkaline dye-bath. It,

however differs from the said alkali blue by imparting in the alkalinebath its character istic purple shade to the material to be dyed, whilealkali blue becomes fixed under the same circumstances in the form ofcolorless saline compounds, which require an aftertreatrnent with acidsin order to develop the characteristic shade.

By passing the material dyed with my new coloring-matter through an acidbath, a slightly brighter shade may be obtained.

What I claim as new, and desire to secure by Letters Patent, is

As a new product, the purple dye-stuff or coloring-matter, which in analkaline bath imparts to the material to be dyed its characteristicpurple shade, and which,when intimately mixed with lime and thensubmitted to destructive distillation, produces a basic oil possessing acharacteristic disagreeable sme1l,substantially as specified Intestimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

CARL LUDWVIG MULLER.

WVitnesses:

HENRY ScHAEPPI, J. F. MONAG'HAN.

